Prepared resin



C A. HQCHWALT PREPARED RES IN Filed June 17, 1950 Patented Mar. 24, 1936 UNlTED rATEs PATENT OFFICE PREPARED RESIN Delaware Application June 17,1930, Serial No. 461,799 10 Claims. (Cl. -260-2) This invention relates to the manufacture of artificial or prepared resins.

One of the principal objects of this invention is to provide such a prepared resin which has 5 characteristics markedly superior in certain 1' spects to the natural resins. I

Another object of the invention is to provide a method for producing a prepared resin this character, which is simple, easily carried out and 1 controlled, economical in the consumption of chemicals, and produces a high, grade resin 0! good color and hardness.

Still another object of the invention is to provide apparatus for ca ry g out the above method and producing the above product.

Other objects and advantages of the'invention will be apparent from the following description when taken in connection with the accompanying drawing and appended claims.

The single view of the drawing is a diagrammatic representation of apparatus for practicing the method, and for producing the resin-like material of the present invention.

Reference is herein made to the copending application of Charles A. Thomas and Carroll A.

Hochwalt, Serial No. 294,491, filed July 21, 1928,

now Patent 1,836,629 which relates to the production of a synthetic resin of this general character.

In the practicing of this invention, unsaturated hydrocarbon compounds are utilized, as for example, unsaturated hydrocarbons found in cracked distillate, such as that obtained from natural gas. Distillate cracked according to the various methods now prevalent, contains a substantial proportion of unsaturated hydrocarbons. While a cracked distillate of relatively uncontrolled character can be employed, it is pre- 40 ferred to use a special fraction of the cracked distillate, which contains substantial proportions of both oleflne and diolefine compounds, such as that fraction passing over between 30 C. and 40 C. While the unsaturated hydrocar- 45 bons employed may be readily obtained from cracked distillate of this character, such compounds obtained from other sources can of course be used.

It is to be understood that the term un- 50 saturated hydrocarbons as used herein, refers to hydrocarbon compounds which unite with other compounds, such, for example, as the halogens, to form addition products without splitting oii a new compound. Unsaturated hydrocarbons are capable of giving the Baeyer test for unsaturatio'n. (Textbook of Organic Chemistry, Holleman, 6th ed page' 131.)

The unsaturated hydrocarbons are placed within a container or polymerizing vessel It],

' which is in turn enclosed within a suitable water 5 jacket it having 'valve controlled inlet and outlet connections l2 and i3 through which water may be flowed for controlling the temperature within, the container. A cover I5 is fastened in a gas tight manner on the upper end of the b vessel, and this cover is provided with a filling opening normally closed by a plug l6 through which material may be supplied to the interior.

' Cover It supports a motor l1, mounted in any is open to atmosphere, as the purpose oi'it is to condense and return to the container iii any vapors that may be generated during the reaction, thus preventing both the loss of-the generated vapors and'the undue building up of pressure during the reaction.

The unsaturated hydrocarbon compounds are fed into the container loithrough a-plpe 25 controlledby a valve 2.6 leading from a suitable source of supply. A suitable catalyst or activating compound, such as pulverized anhydrous aluminum chloride (M2010, is added ,to the un-' saturated hydrocarbons through the opening normally closed by plug It. The aluminum chloride is preferably pulverized as this is found to improve the character of the resultant resin. This material is also added in small quantities at a time, while the contents of the container 40 iii are being agitated by the motor driven stirrer 19. For example, presumingthat 25 gallons of cracked distillate of the fraction 30 to 40 are to be treated within the container l0, and aluminum chloride may be satisfactorily added in quantities or approximately six to eight ounces at a time. With the addition of the first batch of aluminum chloride, there is a rather active chemical reaction, such as a condensation or polymerization, with a resultant rise in temperature. It is desirable to control the temperature of the reaction so that the reacting mass does not become too highly heated. Satisfactory results are secured where the temperature is controlled below 65 (3., this being readily accomplished by introducing the aluminum chloride in small amounts and by supplying cooling liquid to the cooling jacket ll. Additional batches of aluminum chloride are added from time to time as may be done without unduly increasing the temperature within container I0, and this is repeated with continuous agitation until no additional temperature rise results. The amount of aluminum chloride used will depend upon the proportion of condensable unsaturated hydrocarbons, and therefore it is a very satisfactory practice to add aluminum chloride until no further temperature rise is secured. Generally the addition of less than 3 pounds of aluminum chloride for twenty-five gallons of the liquid undergoing polymerization is satisfactory.

In addition to aluminum chloride, other compounds which hydrolyze in water giving an acid reaction will function satisfactorily to cause the conversion of the unsaturated hydrocarbons into resins-for example, chlorides of iron, boron, zinc, antimony, indium, titanium and tin; ,benzene sulfonic acid; propyl alcohol saturated with H01 gas; ethyl sulfate, and aniline hydrobromide. The polymerization is preferably carried out as rapidly as possible while preventing an objectionable temperature rise, as it is found desirable to not leave the catalyst in contact with the material for an objectionably long time. The reaction may proceed as much as twelve hours, but it is preferably completed in less time, such as four to six hours. A thermometer 28 may be mounted in the cover l5 to conveniently indicate the temperature of the reacting mass.

When the reaction within the container I0 is completed, the material is viscous and dark in color. This material is flowed from the polymerizing vessel through the outlet pipe 30 controlled by valve 3l into a neutralizing tank 32 containing a quantity of neutralizing agent. Tank 32 is provided with a tight fitting cover 34 which carries a motor 351 having a shaft 36 extending within the container and carrying at the lower end thereof suitable stirring blades 31. A valve controlled pipe 38 may be used to supply neutralizing liquid from a suitable reservoir to the tank: 32. Various water soluble alkalies might be used for this neutralization, but preferably ammonium hydroxide is employed, as the excess of this material can subsequently be removed by distillation, and it has no injurious effects upon the resulting resin. On the other hand, alkali metal hydroxides such as sodium hydroxide, are more diflicultto remove from the produced resin, and when allowed to remain in the resin form soaps with many of the pigments used in the paint industry and thus interfere with the satisfactory use of the resin with these pigments. A lighter colored product is also generally secured by the. use of ammonia as a neutralizing agent.

" The neutralizing treatment is also preferably carried out in the presence of a non-aqueous organic hydroxy compound which is effective to supply hydroxyl radicals for the decomposition and precipitation of the aluminum chloride or other activating agent present. An alcohol, such as ethyl alcohol, functions very satisfactorily for this purpose. Thus with the quantities specified above, a mixture of about 40% by volume of ammonium hydroxide (28% NI-L) and 60% by volume of ethyl alcohol supplied to the neutralizing tank 32 by pipe 38 until approximately three gallons of the mixture have been introduced, gives very good results. The

stirrer 37 is then started, and the polymerized reaction mass is introduced slowly from container ID in a controlled stream by pipe 30 into the agitated neutralizing agent within the tank 32. The neutralization in the presence of an organic hydroxy compound of this character with proper agitation gives a granular precipitate of aluminum hydroxide which is readily removed by filtration. Otherwise a complex organic aluminum compound is apt to be formed which may remain in the resin giving objectionable results, particularly where the resin is used in varnishes and the like. Ammonia gas may be used, if desired, for the neutralization by leading the NH, gas into the reaction mass containing the hydroxy compound. Or an alcohol or other organic hydroxy compound may be first saturated with NIL gas, and then the ammonia saturated compound used for the neutralization. The term ammonia is used herein to refer to the NHe, either in gaseous form or in solution.

The neutralization could be carried out in the presence of water, but this renders subsequent distillation more difficult, and is apt to result in quantities of water being occluded in the resin at this time. Other organic hydroxy liquids which are miscible with water, such as methyl alcohol, acetone etc., may be used for this purpose. The neutralization is accompanied by a color change, the polymerized product changing from a black or dark red to a yellowish red color, and thus indicating that the neutralization is complete and the mixture basic in character. The agitation and neutralizing action is generally completed in about half an hour. The ammonia neutralizes all of the aluminum chloride present, forming a fiocculent precipitate of aluminumhydroxide. Some of the ammonium chloride formed in the reaction also precipitates in the organic solvents, and a portion of the resin reaction product may also precipitate. In order to insure that the resin is completely dissolved before filtration,

an organic solvent which is immiscible in water,

such as benzol, carbon tetrachloride, ethylene dichloride, and the like, is added to the neutralizing tank 32 prior to filtration. This organic solvent may be present during the neutralizing reaction, and may be initially added to the tank 32 along with the ammonia and the alcohol prior to the introduction of the polymerized reaction mass. Generally the addition of about three gallons of benzcl is sufficient for this purpose.

Tank 32 is provided with a temperature control Jacket 42 having valve controlled inlet and outlet connections 43 and 44 respectively, by means of which a heating medium such as steam or hot water may be supplied to the heating jacket. After the neutralizing reaction is completed, the contents of the tank 32 are preferably heated with steam by Jacket 42 to a temperature of about 60 C. to insure that the produced resin is all dissolved. During this heating action, substantially all the excess ammonia is liberated and passes through the distillate oiftake 45 having control valve 46 to a suitable condenser indicated diagrammatically at 48. This may be a conventional water cooled condenser, having condenser coils with which the pipe 45 communicates, and having an outlet 49 which communicates with branch pipes j ervoir 54, whereas pipe 50 communicates with branches 55 and 58 respectively controlled by valves 31 and 53. Pipe 55 communicates with a vented receiving tank 59 containing water, so that the ammonia passing of! from tank 32 at this time may be dissolved and recovered in tank 59. Pipe 53 communicates with atmosphere, so that gaseous products may be discharged directly to vent, if desired.

The contents of tank 32 are then preferably allowed to settle until stratification into a lower sludge layer, containing the precipitated aluminum hydroxide and ammonium chloride, and a supernatant liquid layer containing the alcohol and benzol and dissolved resin, results. This settling action may properly take place: in three or four hours, but preferably the material is allowed to stand over night. The bottom layer of sludge is then withdrawn by the bottom discharge '2 controlled by valve 63 to a suitable filter Cl, such as a cloth filter. The filter is connected by pipe 65 having a control valve 66 with a receiving or distillation tank 61. The precipitated aluminum hydroxide and ammonium chloride, are thus caught 'on the filter, whereas the filtrate is passed to the distillation vessel 61 through pipe 65. The filtered sludge is preferablytreated to recover aluminum oxide (A120:) and ammonium chloride as by-products. The supernatant liquid, after the withdrawal of the sludge, is then passed by discharge pipe 63 having control valve 63 to a suitable centrifuge or other continuouslyoperating filter to remove any suspended undissolved materials therein, the filtrate passing by pipe H into distillation vessel 81.

Vessel I1 is provided with a tight fitting cover l3 carrying a distillate ofitake pipe ll controlled by valve and communicating with the condenser coil in condenser 48, or with a separate condenser, if desired. A jacket 11, provided with valve controlled inlet and outlet 18 and 19 re-.

spectively for steam or hot water, is provided to exteriorly heat the liquid within vessel 61 to distill oil the more volatile constituents, including the benzol and alcohol. During this distillation, the valves 51 and 58 are closed and valves 15 and 53 are opened, so that the distillate passes through pipe 14 to condenser 43 and the resulting condensate then flows by pipe 51 into receiving or storage tank 54. Distillation is continued until a thermometer in the distillate line rises to approximately 100 C., at which time substantially all of the alcohol and benzol, and any water, will have been driven oi! oi the resulting resin, which -is left in the vessel 61 as a semifiuid or pasty mass. The resin may then be purified to separa higher oils retained therein which tend to render the same soft or putty-like, if a hard resin is desired. This may be accomplished by the introduction of water or steam into the distillation vessel, and then by raising the temperature of the heating jacket 11 to a controlled higher temperature. The temperature is preferably not raised materially above 100 C. without water being present, as the color of the resultant resin may be darkened. Very satis-- factory results are secured, after the initial exterior distillation, by the employment of a steam I distillation. For this purpose, a valve controlled steam inlet 80 is provided, and the cover I3 carries a motor 82 on whose shaft 83 are mounted a plurality of stirring blades or arms 84, which are preferably shaped to conform to the interior wall of the container ll. and are positioned in close proximity thereto to efi'ect a scraping action and prevent the resin from adhering to the wall. Each stirring arm 84 may be provided with a sharpened or pointed edge to facilitate this scraping action.

During this steamdistillation, the knife stirrer is operated to agitate the resin and secure more intimate contact of the steam therewith, as well as to prevent the resin from adhering to the sidev of the vessel with possible overheating. This steam servm to remove and carry oil any remaining benzol End higher oils present in the resin, which materials pass oil by pipe 14. v The condenser coil may be connectedat this time to vent by pipe 56 for the removal of higher boiling gaseous constituentaigiyhile' any benzol or water condensed in condenser 43 passes by pipe 5| into storage tank 64. The steam distillation may be continued for about three to" six hours, and then the valve controlled water drain 88 opened to discharge any water condensed in the bottom of the vessel 6'|,such wateralso containing Impurities dissolved out of theresin. The. steam distillation is then stoppedfand higher pressure steam supplied to jacket 11 to raise the temperature of the resultant mass, the agitation with the knife stirrer being continued. Preferably, the steam pressure in the Jacket 11 is not permitted to rise above to pounds, and the temperature of the mass being treated is controlled below 130 0., generally between 110 C. and 120 C. This final heat treatment, at higher temperatures and agitation may be continued for several hours, thereby removing remaining occluded water from the resin. The resin may be tested by dropping samplesin boiling oil-r and when spattering ceases this shows that the resin, is properly dried. The resin is then removed from the distillation vessel 81, as by the bottom outlet 88, and placed in suitable collecting troughs or vided, a. gravity feed through the entire system,

such as disclosed-herein, is preferred for commercial installations.

The condensate accumulated inthe storage vessel 54 consists primarily of a mixture of benzol and alcohol together with some water. This liquid on standing stratifies into a lower water layer and an upper benzol-alcohol layer. A sight glass 80 is preferably provided to indicate the level of liquid in the vessel and to show "when stratification has taken place. 9| controlled by valve 92 permits the lower water layer to be withdrawn.-while the benzol-alcohol layer is conserved for further use. A portion of this benzol-alcohol mixture'is supplied from time to time by pump 93 through pipe 94 to the neutralizing tank 32 forthg treatment .of fresh batches of polymerized product. Additional make-up alcohol together with ammonia, is added by valve controlled'pipe 33 as needed for the treatmentjof each batch. In plant operation, the'benzol-alcohol mix recovered in the, reservoir 54 soon becomes of sumcient concentration in alcohol so that only ammonia need be added to tank 32 by pipe 33 for the treatment of fresh batches of polymerized product. Thus 7 in plant operation, the only chemicals needed are aluminum chloride and ammonia, the benzol and A bottom outlet unsaturated hydrocarbons of (Ill drawing another portion of the accumulated conde'nsate from storage tank 54 by pipe 95 con-- trolled by valve 88. and introducing this portion;

into a separating tank 97 where an excess of Water is added by pipe 98. The resultant mixed .,liquids on standing then settle out or stratify into two layers, an upper benzol layer containthe unacted upon hydrocarbons, and a lower water-alcohol layer. These layers are separated, such as by decantation, and are separately supplied by pipe 99 to a suitable still or stills I00. which may be of entirely conventional construction. The products are here fractionated to separately recover the alcoholand benzol and other desirable hydrocarbons, these being accumulated in a. suitable collecting vessel indicated at IN. The alcohol thus recovered is preferably returned to the system, such as at the storage tank 54, to maintain the concentration of the alcohol in the benzol-alcohol mixture as described above.

The resin so prepared in accordance with this invention is foimd to have a yellow shading to dark amber color. When dissolved in a suitable oil solvent, such as naphtha, the resin forms a clear amber liquid, which when brushed onto a colorless or has onlya faint yellowish color. The

prepared resin is non-acid in reaction and is un-.

saponifiable. Another very important and desirable characteristic of the prepared resin is that it does not retard the oxidizing action of linseed oil, so that a varnish can be prepared with this resin which compares favorably in speed of drying with lacquers.

While the method herein described and the apparatus for carrying out that method and the product so produced constitute preferred embodiments of our invention, it is to be understood that the invention is not limited to-this precise method or apparatus, or precise product, and that changes may be made therein without departing from the scope of the invention which is defined in the appended claims.

What is claimed is:

1. The method of producing prepared resins, which comprises polymerizing unsaturated hydrocarbons with a metallic halide activating agent which hydrolyzes to give an acid reaction,

and then neutralizing the reaction product with accuse which is immiscible with water, filtering off the undissolved materials, and distilling the resultant filtrate to obtain a solid resin.

3. The method of producing prepared resins, which comprises agitating unsaturated hydrocarbons with a metallic halide activating agent which hydrolyzes to give an acid reaction, neutralizing the resulting resinous reaction product retaining oils having boiling points higher than the boiling points of the original unsaturated hydrocarbons, with an alkaline ammonium compound in the presence of an organic hydroxy compound which acts as a hydrolytic agent to decompose and precipitate the activating agent,

1 adding prior to filtration an organic solvent for resinous reaction product immiscible in wa- -I ter, then filtering the undissolved materials from the neutralized mass, distilling the filtrate to remove organic hydroxy compound, organic solvent and water from the resultant resin, and then introducing steam into the resin to remove retained oils having boiling points higher than the boiling points of the original unsaturated hydrocarbons, and to produce a hard resin.

4. In the production of prepared resinsv by condensation of unsaturated hydrocarbons in the presence of a metallic halide activating agent, followed by neutralization with alcoholic ammonia and removal of the neutralized activating agent, the method of purifying the resinous reaction product which comprises steam distilling the product at a temperature not substantially above 100 C., and then agitating and heating the resultant product at a imperative higher than 100 C. and below 180 Cute drive 01! occluded water.

5. The method of producing prepared resins, which comprises polymerizing unsaturated hydrocarbons with a metallic halide activating agent which hydrolyzes to give an acid reaction, to produce a resinous reaction product, and then neutralizing the reaction product with ammonia in the presence of acetone, to produce a neutralized resinous reaction product readily freed from alkali.

6. The method of producing prepared resins,

which comprises polymerizing unsaturated hydrocarbons with a metallic halide activating agent which hydrolyzes to give an acid reaction to produce a resinous reaction product, then neutralizing the reaction product with ammonia in the presence of an organic water soluble hydrolytic compound to decompose and precipitate the activating agent to produce a neutralized resinous reaction product readily freed from alkali, said compound being selected from the similarly reacting group consisting of methyl alcohol, ethyl alcohol and acetone.

'7. In the manufacture of unsaturated hydrocarbon resins by the polymerization of a cracked petroleum distillate fraction in the presence of a metallic halide activating agent which agent hydrolyzes in water to give an acid reaction, the step of neutralizing the polymerized reaction mixture containingthe metallic halide activating agent by adding thereto a hydrolytic agent consisting of an ammoniacal water soluble alcohol.

8. In the manufacture of unsaturated hydrocarbon resins by the polymerization of a cracked petroleum distillate fraction in the presence of a metallic halide activating agent which agent hydrolyzes in water to give an acid reaction, the

'step of neutralizing the polymerized mixture by emmas I 9. In the manufacture of unsaturated hydr0-.

carbon resins by the polymerization of a cracked liquid petroleum distillate fraction in the presence of a metallic halide polymerizing agent, which agent hydrolyzes in water to give an acid reaction, the step of neutralizing'the polymerized liquid mixture containing the metallic halide polymerizing agent by adding to said reaction mixture an aqueous ammoniacal alcoholic solu- 6 tion.

10. In the polymerization of cracked petroleum distillates to produce resinous polymers wherein aluminum chloride is used as the polymerizing agent, the step in the recovery of the polymerized product, characterized in that the polymerized mixture is subjected to the' action of aqueous alcoholic ammonia, whereby complete neutralization and. decomposition! the aluminum chloride, is effected ieeeyerlns the resinous polymeraf Y 4 

